Imageable diacetylene ethers

ABSTRACT

This application relates to monomers and homopolymers of diacetylenic ethers having the formula ##STR1## wherein X is alkyl, alkenyl, aryl, alkaryl, aralkyl, aralkenyl, monoalkylamino or dialkylamino and Y is alkyl, alkenyl or ##STR2## where X&#39; is independently selected from the group of X. The invention also relates to the method of preparing and using said alkoxy diacetylenes.

This is a division of application Ser. No. 601,499, filed Oct. 23, 1990,now U.S. Pat. No. 5,094,134.

In one aspect this invention relates to novel diacetylene ethers andhomopolymers thereof. In another aspect the invention relates tovisually imageable monomers and homopolymers which have significantlyimproved sensitivity to energy transmitted at a short wavelength of200-350 nm as characterized by photon and particulate radiation and at awavelength within the 400-1,500 nm range as characterized by lasers, arclamps, etc. Another aspect relates to high speed data recording byexposure to radiation. Still another aspect of the invention relates tothe preparation of the present diacetylenic ethers.

BACKGROUND OF THE INVENTION

Diacetylenic and other polyacetylenic compounds have been used asrecording layers for optical discs and similar information storagedevices. However, there is a lack of commercially available economicalchemicals needed for their preparations. Propargyl alcohol is the onlyavailable industrial chemical with a terminal acetylenic functionality.However, diacetylenic chemicals prepared from propargyl alcohol are soinactive that they are impractical for commercial use in recordingmedia. Accordingly, it is an aim of research to discover chemicalprocesses which can be efficiently and economically effected to provideimageable polyacetylenes and their homopolymers.

The development of a visual image which requires exposure at shortwavelengths, excludes the economical and efficient laser imaging, sinceprior polyacetylene compounds are generally incapable of absorbingenergy and undergoing polymerization when exposed to light inwavelengths above about 400 nm. Visual images are those images which areclearly recognizable by the human eye and are characterized by highoptical contrast in one or more of the red, green and blue portions ofthe spectrum. By high optical contrast is meant an optical densitydifference of at least 1.0 between the maximum density and minimumdensity portions of the image, where optical density is defined as log₁₀(1/transmittance) for transmitted light and log₁₀ (1/reflectance) forreflected light. Such visual imaging is significantly distinguished fromprior data recording where image contrast is relatively low and noteasily discernable by the human eye or without high magnification. Inseveral cases laser imaging at wavelengths above 400 nm, based on thethermal color change of the polyacetylenic compound to develop a usefulvisual image, has been attempted, but it has been found that cumbersomehigh-output equipment, e.g. argon, metal-vapor or gas lasers and thelike are required. Relatively low-output lasers, in the 650-1,500 nmwavelength range, fail to imprint on either known polyacetylenes ortheir polymers, particularly in relatively thick layers required toproduce useful visual images as opposed to the relatively thin layersneeded for digital data recording.

Short wavelength imaging of prior polyacetylenic compounds is alsoaccompanied with several drawbacks and disadvantages, among which is alack of color stability at the lower color transition temperatures ofthe thermochromic compound Also, compounds of significantly greatersensitivity are needed for high definition and contrast in recordingdata and for production of sharp reproducible images Accordingly, it isthe aim of research, with consideration to cost performance andproduction efficiency, to provide an organic system most suitable forvisual imaging and optical data recording, which is imageable at anoutput energy in the 650-1,500 nm wavelength range characteristic ofcompact semi-conductor diode lasers or in the short wavelength rangecharacteristic of radiation by UV light, electron beam, α-particles,X-rays, γ-rays, neutrons, etc.

It is an object of this invention to provide a thermochromic orphotochromic compound which answers the above needs and which hasincreased sensitivity to imaging with a compact semi-conductor laser ina wavelength of at least 400 nm or with short wavelength radiation inthe 200 to 350 nm range, by a process which has low cost, highperformance and high production efficiency.

Another object of this invention is to provide an economical processcapable of producing imageable diacetylenic ethers.

Another object of the invention is to provide a transmitted image by alow cost high efficiency process.

Still another object of the invention is to provide an imageablethermosensitive polyacetylene which is receptive to wavelengths up toabout 1,500 nm and to a recording film utilizing said polyacetylene.

These and other objects of the invention will become apparent from thefollowing description and disclosure.

THE INVENTION

In accordance with this invention there is provided an imageablethermochromic diacetylene ether having significantly improvedsensitivity which is defined by the formula ##STR3## wherein X is aradical having from 1 to 22 carbon atoms and is selected from the groupof alkyl, alkenyl, aryl, alkaryl, aralkyl, aralkenyl, monoalkylamino anddialkylamino and Y is alkyl or alkenyl having from 1 to 22 carbon atomsor --CH₂ OCH₂ CH₂ OOCX' where X' is independently selected from thegroup of X.

Of the above diacetylene ethers, the symmetrical diacetylene ethermonomers wherein X is a C₂ to C₁₀ alkylene, carbamate, phenyl or styrylradical, and the homopolymers derived from said monomers, are preferred.

Specific examples of the present diacetylenes include

3,10-dioxa-5,7-dodecadiyn-1,12-bis(n-butylcarbamate),

1,12-(3,10-dioxa-5,7-dodecadiynediyl)dicinnamate,

3,10-dioxa-5,7-dodecadiyn-1,12-bis(n-propylcarbamate),

3,10-dioxa-5,7-dodecadiyn-1,12-bis(ethylcarbamate),

3,10-dioxa-5,7-dodecadiyn-1,12-bis(phenylcarbamate),

1,12-(3,10-dioxa-5,7-octadiynediyl)dibenzoate,

3,10-dioxa-5,7-dodecadiyn-1,12-bis(n-octyl carbamate),

3,10-dioxa-5,7-dodecadiyn-1,12-bis(n-octadecyl carbamate),

3,10-dioxa-5,7-dodecadiyn-1,12-bis(isopropyl carbamate),

3,10-dioxa-5,7-dodecadiyn-1,12-bis(methyl carbamate),

3,10-dioxa-5,7-dodecadiyn-1,12-bis(cyclohexyl carbamate),

3,10-dioxa-5,7-dodecadiyn-1,12-bis(2-methylcarbamyl phenyl carbamate),

3,10-dioxa-5,7-dodecadiyn-1,12-bis[3-(methylamino) carbamyl phenylcarbamate],

1,12-(3,10-dioxa-5,7-dodecadiyne)diyl-di(m-aminobenzoate) and theircorresponding homopolymers.

The present ether compounds possess superior photographic properties asobserved in their high sensitivity, rapid color transition and highimage acuity. As imaging agents, the above diacetylenic ether monomerscan be employed individually or in admixtures and such mixtures cancomprise combinations of monomers or mixtures of monomeric andhomopolymeric compounds of the same or different species. Also thehomopolymers themselves may be employed individually or as intermixturesto provide the superior imaging agents of this invention.

As shown hereinafter, diacetylenes prepared by reactions involvingpropargyl alcohol do not provide sensitive photochromic products whichare useful as recording media. It is now found that ethoxylatedpropargyl alcohol derivatives can be used to produce diacetylene ethersof unexpectedly high sensitivity to short wavelength radiation, e.g. UVlight or electron beam exposure and that the homopolymers of suchdiacetylene ethers achieve permanent color stability and possess highsensitivity to longer wavelength exposure by laser radiation. Thesymmetrical diacetylene ethers of this invention are prepared by thereaction of an ethoxylated propargyl alcohol having the formulaHC.tbd.CCH₂ OC₂ H₄ OH with an organic isocyanate, RNCO, an ester RCOOR'or a carbamate R(R")NCOOR' wherein R' at least one of R and R" is aradical having from 1 to 20 carbon atoms and is selected from the groupof alkyl, alkenyl, aryl, alkaryl, aralkyl and aralkenyl and one of R andR" can be hydrogen to produce the corresponding monoacetylene. Themonoacetylene intermediate is then subjected to oxidative coupling withoxygen in the presence of a catalyst, such as cuprouschloride-tetramethylene ethylene diamine. These reactions areillustrated by the following equations: ##STR4##

The unsymmetrical diacetylene ethers are prepared by coupling reactionsinvolving the intermediate III above and an acetylenic iodide,exemplified as follows: ##STR5##

The above reactions are carried out at a temperature of between about30° and 180° C. under up to about 50 psig for a period of from about 1to about 40 hours; preferably at a temperature of between about 80° andabout 150° C. for a period of from about 2 to about 20 hours.Stoichiometric amounts of reactants I and II or a slight molar excess ofcoreactant II, e.g. 1:1.2 is employed in the above reaction shown in A.

The homopolymers of the polyacetylene ethers are prepared by subjectingthe monomer to radiation in the short wavelength regions of theelectromagnetic spectrum.

Where the homopolymer is to be used as a modulating film for imagingmaster printing plates or printed circuit boards, the homopolymer issubjected to heat, e.g. as generated by radiation emissions at a longerwavelength from a laser or a light source of similar wavelength above400 nm, such as from a xenon arc lamp, a mercury arc lamp, atungsten-quartz halogen lamp.

In such applications, e.g. when recording data for transmission to amaster printing plate or printed circuit board, it is most desirable toselect a diacetylenic ether monomer which undergoes a chromic changewhich dramatically increases the absorption of blue light (e.g. achromic change to yellow) since this color change provides the highestcontrast for duplication to other photosensitive recording media,particularly those containing photopolymers sensitive to blue andultraviolet light as are commonly employed in commercialphotolithographic printing plates and etch resists used in thepreparation of printed circuit boards. The1,12-(3,10-dioxa-5,7-dodecadiyne)diyl dicinnamate of this invention,having the formula

    [H.sub.5 C.sub.6 --CH═CH(CO)OC.sub.2 H.sub.4 OCH.sub.2 --C.tbd.C].sub.2,

is such a compound. However, diacetylene ether monomers and homopolymerswhich are converted to other hues or hue intensities in the blue, red,magenta, green, brown and other color spectra all provide good imagedefinition.

Coatings of the present diacetylene materials for application on asubstrate are conveniently prepared from aqueous dispersions wherein thediacetylene ether monomers, having an average crystalline diameter ofbetween about 0.02 um and about 5 um, preferably between about 0.1 umand about 1 um, are dispersed in a binder solution, preferably anaqueous binder solution, to provide a dispersion, emulsion or suspensioncontaining from about 1 to about 50 wt. % solids, preferably from about4 to about 15 wt. % solids. The liquid dispersion of diacetylene ethermonomer may then be coated on a substrate and dried. Alternatively, finehomopolymerized particles in a similar dispersion can be coated on thesubstrate and dried to provide the imageable film of this invention.Other coating alternatives to the dispersion layer coating include thedeposition of one or more monomolecular layers of the diacetylene ethermonomer and/or homopolymer as is carried out by the Langmuir-Blodgettetechnique, spin or spray coating methods.

Suitable diacetylene ether substrates include polyethyleneterephthalate, nylon, polystyrene, cellulose acetates, cellulosenitrate, cellophane, polyvinyl chloride, polyvinylidene chloride,teflon, polychlorotrifluoroethylene, polyethylene, polypropylene, paper,ceramic, glass, metal, wood and the like.

For the purposes of the present invention, the image receptive layer isusually the surface layer of the imaging film; however, a protectivelayer can be applied over the diacetylene ether surface layer, e.g. toprevent damage due to abrasion, moisture, etc. Liquid dispersion ofnormally crystalline diacetylenic ethers may be aged before drying onthe substrate according to the process disclosed in U.S. Pat. No.4,734,355.

Exemplary of binder materials for use in dispersions include natural andsynthetic plastics, resins, waxes, colloids, gels and the like includinggelatins, desirably photographic-grade gelatin, various polysaccharidesincluding dextran, dextrin, hydrophilic cellulose ethers and esters,acetylated starches, natural and synthetic waxes including paraffin,beeswax, polyvinyl-lactams, polymers of acrylic and methacrylic estersand amides, hydrolyzed interpolymers of vinyl acetate and unsaturatedaddition polymerizable compounds such as maleic anhydride, acrylic andmethylacrylic esters and styrene, vinyl acetate polymers and copolymersand their derivatives including completely and partially hydrolyzedproducts thereof, polyvinyl acetate, polyvinyl alcohol, polyethyleneoxide polymers, polyvinylpyrrolidone, polyvinyl acetals includingpolyvinyl acetaldehyde acetal, polyvinyl butyraldehyde acetal, polyvinylsodium-o-sulfobenzaldehyde acetal, polyvinyl formaldehyde acetal, andnumerous other known photographic binder materials, or mixtures ofbinder materials, including a substantial number of aforelisted usefulplastic and resinous substrate materials which are capble of beingplaced in the form of a dope, solution, dispersion, gel, or the like forincorporation therein of the thermosensitive polyacetylenic polymer andcapable of processing to a solid form containing dispersed crystals ofthe thermosensitive crystalline polyacetylenic polymer. As is well knownin the art in the preparation of smooth uniform continuous coatings ofbinder materials, there may be employed therewith small amounts ofconventional coating aids as viscosity controlling agents, surfaceactive agents, leveling agents dispersing agents and the like.

The dried imageable, monomeric diacetylene ether film of this inventionis subjected to exposure by radiant photon, ionizing or particulateenergy transmitted at a wavelength of between about 200 and about 350 nmto effect an immediate color change, or a discernable change in colorintensity, by homopolymerization of the monomer. This short wavelengthexposure can be effected with UV light, α-particles, X-rays, γ-rays,β-rays, an electron beam, neutrons, a xenon flash lamp, a mercury arclamp, a tungsten quartz, halogen lamp, actinic light, a UV laser e.g. anargon ion, a krypton ion or a GaAlP laser, and the like. For example,when using an electron beam, the image receptive layer is subjected to adosage of between about 10⁻¹⁰ and about 10⁻¹ coulomb/cm² (C/cm²),preferably between about 10⁻⁸ and about 10⁻³ C/cm², or equivalent dosagefor other sources of particulate or photon energy radiation, to producean immediate image of distinguishable color or color intensity.Generally short wavelength energies of between about 10 and about 50 KeVcan be employed to image the polyacetylene diethers of this invention.

Specific techniques of short wavelength recording are well known, thusfurther amplification is not required. However, for illustrativepurposes, a conventional electron beam recording operation suitable forthe present invention may utilize an electron beam characterized byhaving a beam diameter of from about 1 to 100 micrometers, an energy offrom about 10 to 30 KeV, a current flow of from about 10⁻⁹ to 10⁻⁵ ampsand adapted to scan a target area at a rate such that the dwell time isfrom about 10⁻⁸ to 10⁻³ seconds. Vacuum pressures in the film chambercommonly range from about 10⁻³ to 10⁻⁸ torr.

When a homopolymer of the diacetylene ether is applied as the imageablelayer on a substrate, it is directly imaged in a particular pattern ordesign, with a laser in the writing mode generating energy at awavelength of above 400 nm. Lasers such as semi-conductor, solid state,gas, metal-vapor and dye lasers in pulsed or continuous wave can beused, although semi-conductor diode lasers having an output power offrom about 1 microwatt to 10 watts are preferred. Specific examples ofsuitable lasers include GaAlAs, NaYtAl garnet, Ar, He-Ne, He-Cd, GaAsNeYAl garnet, ruby, NaYAg, krypton ion, copper vapor lasers, etc.

Lasers, or other light sources, transmitting energy above 400 up to1,500 nm or more wavelength provide thermal imaging at high imageresolution, which is an important consideration when recording data.Within the wavelength range of 600 to 1,500 nm, high speed can beachieved as well. For example, using a lser beam diameter of 0.5 to 2um, an exposure time of 180-250 ns/dot and output of 2.5-3.5 mW, animage is encoded on the diacetylene ether homopolymer which hasexcellent resolution and high color contrast. Generally the speed ofrecording and density varies directly with the output power of the laserand the thickness of the polymer coating. Accordingly, thin coatings offrom about 0.02 to 100 micrometers, preferably from about 0.1 to 5micrometer are recommended, whereupon the optical density change withinthe imaged area is from about 1.0 to greater than 5.0 density units andpreferably from about 1.5 to about 4.5 density units.

It is to be understood that the polymeric diacetylenic ethers areusually highly colored and strongly absorb radiation across a broadrange of the visible spectrum from 400-650 nm. However, it is also to beunderstood that in cases where a certain homopolymer does not absorbradiation in the wavelength of a given laser emission, a suitable energyabsorbing compound is used in conjunction with the homopolymer in thecoating to absorb energy from the laser and to generate heat generallyin excess of 50° C., preferably in excess of 80° C., for effecting thethermal color change or change in color intensity in the impingedportions of the thermochromic diacetylene ether homopolymer. Such energyabsorbing compounds are generally needed to inscribe a homopolymer whenthe wavelength of the laser radiation is more than about 650 nm or whenit is desirable to encode the diacetylene ether monomer at energies inexcess of 380 nm wavelength.

Suitable energy absorbing compounds include complex and quaternized dyessuch as the polycarbocyanine dyes disclosed in copending U.S. patentapplication Ser. No. 07/601,537 entitled LASER IMAGEABLE COMPOSITIONincorporated herein by reference. Other suitable energy absorbing dyesinclude metal complexes such as diimine iron complex, dithiol nickelcomplex, indigo, anthraquinone, azulenium, polycarbocyanine, squarylium,indolizinium, naphthalocyanine, naphthoquinone and its analogs,phthalocyanine, polymethine, pyrylium, thiapyrylium, telluropyrylium,triaryl ammonium, triquinocycloalkane, or the specific dyes disclosed inthe Journal of Imaging Science, Volume 32, number 2, March/April 1988,pages 51-56 (ORGANIC ACTIVE LAYER MATERIALS FOR OPTICAL RECORDING byJames E. Kuder); Chemistry in Britain, November 1986, pages 997-1000(MODERN DYE CHEMISTRY by J. Griffiths); Angewandte Chemie, Volume 28,number 6, June 1989, pages 677-828 (SEARCH FOR HIGHLY COLORED ORGANICCOMPOUNDS by Jurgen Fabian et al.); Journal of Imaging Technology,Volume 12, Number 3, June 1986, pages 140-143, (ORGANIC MATERIALS FOROPTICAL DATA STORAGE MEDIA--AN OVERVIEW by James E. Kuder), andKirk-Othmer's Encyclopedia of Chemical Technology, Second Edition, Vol.6, pages 605-609 and 611-624, all incorporated herein by reference.

As a guide for the selection of an energy absorbing compound in awavelength similar to transmission of a particular imaging device, thefollowing table provides specific examples of wavelength absorbance.However, these dyes are in no way limiting to the scope of energyabsorbing compounds useful in this invention.

                  TABLE                                                           ______________________________________                                        Dye               Wavelength Absorption                                       ______________________________________                                        Aromatic annulenes                                                                              768 nm                                                      Al tetraazaporphyrins                                                                           1204 nm                                                     Ni dithiolenes    1298 nm                                                     Streptopolymethines                                                                             1500 nm                                                     Silenoxanthenylium                                                                              802 nm                                                      Azo               778 nm                                                      Indophenols and Analogues                                                                       761 nm                                                      Thermochromic dianthrone                                                                        675 nm                                                      Betaines          934 nm                                                      Divinyl benzothiazole                                                                           640 nm                                                      Trivinyl benzothiazole                                                                          750 nm                                                      Diethyl carbocyanine iodide                                                                     700 nm                                                      ______________________________________                                    

Preferred of the above compounds are the water soluble dyes, mostpreferably the water soluble polycarbocyanine dyes. It is also to beunderstood that mixtures of these dyes can be employed. For example,1:20 to 20:1 mixtures of polycarbocyanine and squarylium dye mixturesare useful and can provide the energy absorption and heat needed tothermally activate the thermosensitive dialkoxy polyacetylenehomopolymer at these higher wavelength transmissions. When needed, theenergy absorbing adjuvant is added and intimately mixed in thedispersion prior to coating and drying on the substrate. The amount ofdye employed is sufficient to provide a peak optical density of betweenabout 0.1 and about 3, preferably between about 0.2 and about 2, in thedried coating. In cases where the dye is not water soluble it can bedissolved in a suitable inert solvent such as a ketone, alcohol, ester,hydrocarbon etc. and the like for addition to the dispersion. The mostpreferable solvents are those which are water miscible.

In such cases where an energy absorbing dye is employed, the weightratio of homopolymer to dye can vary between about 1000:1 and about1:10, depending upon the amount of homopolymer present and the amount ofradiation energy needed to be converted to heat energy. Most often thedye comprises between about 0.005 and about 1 wt. % of the imagingcompound.

With regard to imaging techniques, the short wavelength exposure fromabout 200 to about 350 nm, can be employed to homopolymerize all or aportion of the colorless diacetylene ether monomer, i.e. a shortwavelength transmitting device can be used to homopolymerize the entirecolorless monomer (case a) or the monomer can be scribed, in one orseveral steps, to define a predetermined pattern or image with a shortwavelength transmitting device, operated in the writing mode, (case b).In case (a), the entire film acquires chromic change associated with theparticular homopolymer; whereas in case (b) a homopolymerized chromicimage is inscribed on the colorless background of the unexposed monomer.In case (a) the laser generating energy in a wavelength above 400 nm isemployed in the writing mode to inscribe a predetermined permanent imageof a distinguishable color on the contrasting colored homopolymer layer.In case (b), the laser generating at the longer wavelength can besynchronized with the scribing device operating at the short wavelengthand used in the writing mode to retrace the previously inscribed imageor it can be used to expose the entire polymerized and non-polymerizedportions of the diacetylene ether layer so as to induce a permanentchromic change to the preinscribed image on a colorless background.

Having thus generally described the invention, reference is now had tothe following examples which illustrate preferred embodiments but whichare not to be construed as limiting to the scope of the invention whichis more broadly defined above and in the appended claims.

EXAMPLE 1 3,10-dioxa-5,7-dodecadiyn-1,12-bis(n-propyl carbamate)

2-(Propargyl) ethanol (100 g, 1 mole), tetramethylethylenediamine (30 g)and tetrahydrofuran (THF) (400 ml) were charged into a 1-liter flaskwhich was equipped with a mechanical stirrer, thermometer, gas inlet,and a dry ice condenser. The solution was brought to 50° C. under ablanket of nitrogen. A solution of n-propyl isocyanate (112 g, 1.2moles) and THF (50 ml) was added through a dropping funnel to the abovesolution which was vigorously stirred over a period of one hour at 50°to 55° C. The resulting solution was held for 23 hours at thistemperature and then cooled to 40° C. Cuperous chloride (3 g) was thenadded and oxygen was bubbled through the solution at 40-45° C. for 23hours after which the solvent was stripped off under vacuum and theremaining solid material was washed twice with 300 ml of 10% HCl, twicewith 300 ml of distilled water and air dried to give 165.4 g of3,10-dioxa-5,7-dodecadiyn-1,12-bis(n-propyl carbamate); m.p. 93-94° C. Aone gram sample of the colorless crystalline product was spread on afilter paper and subjected to a UV irradiation at 254 nm. In less than 1second the colorless, crystalline product homopolymerized to a darkpurple. Upon heating on a hot plate, the purple polydiacetyleneunderwent a thermochromic change to a permanent red color.

EXAMPLE 2 3,10-dioxa-5,7-dodecadiyn-1,12-bis(ethyl carbamate)

3,10-dioxa-5,7-dodecadiyn-1,12-bis(ethyl carbamate) was preparedfollowing the same procedure as for the preparation of3,10-dioxa-5,7-dodecadiyn-1,12-bis(n-propyl carbamate) in Example 1except that ethyl isocyanate was substituted for n-propyl isocayanate.The 3,10-dioxa-5,7-dodecadiyn-1,12-bis(ethyl carbamate) productrecovered has a melting point of 105-107° C.

A one gram sample of the crystalline product was spread on a filterpaper and subjected to a UV irradiation at 254 nm. Within less than onesecond, the colorless crystalline solid product homopolymerized to ablue color which, upon heating on a hot plate, underwent a thermochromicchange to a permanent red color.

EXAMPLE 3 3,10-dioxa-5,7-dodecadiyn-1,12-bis(isopropyl carbamate)

A 180 g sample of 3,10-dioxa-5,7-dodecadiyn-1,12-bis(isopropylcarbamate) was prepared following the same procedure as for thepreparation of 3,10-dioxa-5,7-dodecadiyn -1,12-bis(n-propyl carbamate)in Example 1 except that isopropyl isocyanate was substituted forn-propyl isocayanate. The 3,10-dioxa-5,7-dodecadiyn-1,12-bis(isopropylcarbamate) product recovered has a melting point of 82-85° C.

A one gram sample of the crystalline product was spread on a filterpaper and subjected to a UV irradiation at 254 nm. Within less than onesecond, the colorless crystalline solid product homopolymerized to apink color which, upon heating on a hot plate, underwent a thermochromicchange to a permanent golden yellow color.

EXAMPLE 4 3,10-dioxa-5,7-dodecadiyn-1,12-bis(n-butyl carbamate)

2-(Propargyl) ethanol (1.5 mole), tetramethylethylenediamine (30 g) and(THF) (500 ml) were charged into a 2-liter flask which was equipped witha mechanical stirrer, thermometer, gas inlet, and a dry ice condenser.The solution was brought to 60° C. under a blanket of nitrogen. Asolution of n-butyl isocyanate (1.65 moles) and THF (200 ml) was addedthrough a dropping funnel to the above solution which was vigorouslystirred over a period of one hour at 60° to 68° C. The resultingsolution was held for 3 hours at this temperature and then cooled to 40°C. Cuperous chloride (10 g) was then added and oxygen was bubbledthrough the solution at 40-45° C. for 20 hours after which the solventwas stripped off under vacuum and the remaining solid material waswashed twice with 300 ml of 10% HCl, twice with 300 ml of distilledwater and air dried to give 389.6 g of3,10-dioxa-5,7-dodecadiyn-1,12-bis(n-butyl carbamate); m.p. 80-82° C. Aone gram sample of the colorless crystalline product was spread on afilter paper and subjected to a UV irradiation at 254 nm. In less than 1second the colorless, crystalline product homopolymerized to a darkpurple. Upon heating on a hot plate, the purple polydiacetyleneunderwent a thermochromic change to a permanent red color.

EXAMPLE 5 A. Preparation of [C₆ H₅ CH═CH--COOC₂ H₄ OCH₂ --C.tbd.C--]₂ -

Trans methyl cinnamate (324.4 g, 2 moles), 2-(propargyloxy) ethanol(200.1 g) and concentrated sulfuric acid (1 ml) were charged into aone-liter flask equipped with a mechanical stirrer, a thermometer, anitrogen inlet and an adapter connected to a condenser. The solution washeld at 110° C. over night under a flowing stream of nitrogen to removemethanol by-product. The remaining liquid was then vacuum distilled anda center cut of 280.7 g was collected at 147° C. and 0.01 mm Hg. The2-(propargyloxy) ethanol product in 98% purity was recovered andidentified by IR and nmr analysis.

2-(Propargyloxy) ethanol (78.1 g), tetrahydrofuran (340 ml), tetramethylethylene diamine (20 g) and cuperous chloride (3 g) were charged into aone-liter flask. A stream of oxygen was bubbling through the solutionwith vigorous stirring for 11 hours at 40-45° C. The tetrahydrofuransolvent was then stripped off. The crude product was washed two timeswith 300 ml of 10% HCl solution and two times with water. After beingdried in air, 72.5 g of 2-(propargyloxy) ethyl cinnamate, m.p. 62-65° C.was obtained. The structure of the chemical was identified by nmr and IRanalyses.

B. Preparation of Coating Dispersion

In a glass container, 1.2 g. of the above product were dissolved atabout 50° C. in 3.6 g. of ethyl acetate and the resulting solution wasfiltered and designated Solution A. A second solution, designatedSolution B, was prepared by dissolving 1.2 g. of photographic gelatinand 0.05 g. of ALKANOL XC (an alcohol-containing wetting agent, suppliedby E. I. duPont) in 30 g. of water. Solution B was heated to 60° C. andintroduced into a 250 ml Waring Blender. While blending at high speed,Solution A was added to Solution B after which the blending wascontinued for 2 minutes. The resulting mixture was then poured into acrystallizing dish to chill set at about 12° C. The resulting gelleddispersion was then cut into approximately 1 cm cubes and allowed towarm in an air stream at approximately 32° C. to remove ethyl acetate byevaporation. After the ethyl acetate had been removed the gelleddispersion was reconstituted by melting at 40° C. and adding sufficientwater to replace the weight loss that occurred during drying.

C. Coating a Film Base with Dispersion

The reconstituted dispersion was coated at about 8 micrometers thicknesson a poly(ethylene terephthalate) film base which had been overcoatedwith a 1 micrometer thick layer of an adhesion promoting materialcomposed of about 50 wt. % gelatin and 50 wt. % of a latex polymer. Thecoated film was then allowed to dry in air at ambient temperature.

D. Imaging the Film

A 4×4 inch sample of the above film was placed in a holding device overwhich is mounted a low pressure mercury arc lamp having a 100 wattoutput and emitting UV radiation at a maximum wavelength of about 253.7nm. The colorless film is exposed for 0.1 second to emissions from thelamp so as to absorb energy and polymerize colorless [C₆ H₅ --CH═CHCOOC₂H₄ OCH₂ C.tbd.C₂ to a rich magenta homopolymer.

The resulting homopolymer is then scribed with a copper vapor laserhaving an output of 3 watts which transmits energy at about 560 nmwavelength and impinges discrete areas of the surface of the filmdefined by a series of diamond shaped figures and lines. The energygenerated by this transmission is absorbed by the homopolymer and heatsthe exposed areas of the film to a temperature of about 65° C. in afraction of a second whereby an image of said diamond shaped figures andlines is transmitted in high acuity in a permanent bright yellow coloron the magenta background which is not exposed to the laser emissions.

E. Use of the Yellow Imaged Film as a Modulating Film

The above sample is employed as a modualting film in the following test.A blue light source, i.e. a high pressure mercury arc lamp operating atan output power of 1 kilowatt and transmitting energy in a wavelength of350-450 nm is focused to scan the entire area of the film sample whichis positioned about 3.6 feet from the light outlet. Contiguous with thesurface of the film and on the surface directly opposite the surfacebeing radiated, is positioned the imageable surface layer, i.e.4-diazodiphenylamine/formaldehyde condensate, supported on cellulosetriacetate sheet of the photoresist master printing plate.

The blue light from the lamp is absorbed in the imaged areas of the filmsample and is transmitted from the non-imaged areas, in an exactnegative imaged pattern to the imageable surface layer of thephotoresist where it attacks the polymer condensate and renders thedecomposed areas insoluble in water.

EXAMPLE 6 2,4-hexadiyn-1,6-bis(n-butyl carbamate)

Propargyl alcohol (104.9 g, 1.9 moles), tetramethylethylenediamine (28.1g) and (THF) (365.5 ml) were charged into a 1-liter flask which wasequipped with a mechanical stirrer, thermometer, gas inlet, and a dryice condenser. The solution was brought to 40° C. under a blanket ofnitrogen. A solution of n-butyl isocyanate (222.7 g, 2.3 moles) and THF(93 ml) was added through a dropping funnel to the above solution whichwas vigorously stirred over a period of one hour at 40° to 45° C. Theresulting solution was held for 18 hours at this temperature. Cuperouschloride (8 g) was then added and oxygen was bubbled through thesolution at 40-45° C. for 28 hours after which the solvent was strippedoff and the remaining solid material was washed twice with 300 ml of 10%HCl, twice with 300 ml of distilled water and air dried to give 280.5 gof 2,4-hexadiyn-1,6-bis(n-butyl carbamate). The colorless, crystallineproduct has a m.p. of 55-60° C. A one gram sample of the colorlesscrystalline product was spread on a filter paper and subjected to a UVirradiation at 254 nm. After 2 seconds only a slight color change couldbe detected indicating that this product would be unsuitable forphotoimaging.

EXAMPLE 7 2,4-hexadiyn-1,6-bis(ethyl carbamate)

A 176 g. sample of 2,4-hexadiyn-1,6-bis(ethyl carbamate) was preparedfollowing the same procedure as for the preparation of2,4-hexadiyn-1,6-bis(n-butyl carbamate) in Example 6 except that ethylisocyanate was substituted for n-propyl isocayanate. The2,4-hexadiyn-1,6-bis(ethyl carbamate) colorless crystalline productrecovered has a melting point of 93-94° C.

A one gram sample of the product was spread on a filter paper andsubjected to a UV irradiation at 254 nm. After 5 seconds, the colorlesscrystalline product homopolymerized to a magenta color. Upon heating thehomopolymer on a hot plate the product gradually darkened. Because ofthe slow reactivity to the homopolymer and the lack of a sharpthermochromic change, this product is unsuitable for photoimaging.

EXAMPLE 8 2,4-hexadiyn-1,6-bis(n-propyl carbamate)

A 281 g sample of 2,4-hexadiyn-1,6-bis(n-propyl carbamate) was preparedfollowing the same procedure as for the preparation of2,4-hexadiyn-1,6-bis(n-butyl carbamate) in Example 6 except thatn-propyl isocyanate was substituted for n-butyl isocayanate. The2,4-hexadiyn-1,6-bis(n-propyl carbamate) colorless, crystalline productrecovered has a melting point of 115-117° C.

A one gram sample of the product was spread on a filter paper andsubjected to a UV irradiation at 254 nm. After 30 seconds, no colorchange was observed, accordingly this product is unsuitable forphotoimaging.

EXAMPLE 9 2,4-hexadiyn-1,6-bis(isopropyl carbamate)

A 28 g sample of 2,4-hexadiyn-1,6-bis(isopropyl carbamate) was preparedfollowing the same procedure as for the preparation of2,4-hexadiyn-1,6-bis(n-butyl carbamate) in Example 6 except thatisopropyl isocyanate was substituted for n-butyl isocayanate. The2,4-hexadiyn-1,6-bis-(isopropyl carbamate) colorless, crystallineproduct recovered has a melting point of 138-140° C.

A one gram sample of the product was spread on a 5 inch filter paper andsubjected to a UV irradiation at 254 nm. After 30 seconds no colorchange was observed, indicating that this product is unsuitable forphotoimaging.

EXAMPLE 10 2,4-hexadiyn-1,6-diyl dicinnamate

2,4-Hexadiyn-1,6-diol (66.1 g, 0.6 mole), triethylamine (70 g) and (THF)(400 ml) were charged into a 1-liter flask which was equipped with amechanical stirrer, thermometer, gas inlet, and a dry ice condenser. Thesolution was brought to 50° C. under a blanket of nitrogen. A solutionof cinnamoyl chloride (110 g, 0.6 moles) and THF (200 ml) was addedthrough a dropping funnel to the above solution which was vigorouslystirred over a period of one hour at 45° . The resulting solution washeld for 5 hours at this temperature and then heated to 55° C. and heldat this temperature for an additional 20 hours to complete the reaction,after which the THF was stripped off and the remaining solid wasredissolved in 500 ml of toluene. The toluene solution was washed threetimes with water, dried over magnesium sulfate and filtered After thetoluene was removed from the filtrate, 134 g. of the colorless,crystalline 2,4-hexadiyn-1,6-diyl dicinnamate product having a m.p. of102-104° was identified by NMR and IR analyses. One gram of thedicinnamate was spread on a filter paper and subjected to UV irradiationat 254 nm. After 30 seconds, no color change was observed; indicatingthat this product is unsuitable for photoimaging.

EXAMPLE 11

Example 5 is repeated except that in Part B, 0.1 wt. % of IR-125 dye (apolycarbocyanine dye supplied by Eastman Kodak) is added to solution Band a GaAlAs semiconductor diode laser with a wavelength of about 830 nmis substituted for the copper vapor laser in Part D. The image producedis one of high resolution defined in a bright yellow color on a magentacolored background.

EXAMPLE 12

Example 5 is repeated except that in part D, an electron beam writingdevice is used in place of the high pressure mercury arc lamp. Theelectron beam is used to instantly homopolymerize diacetylene and towrite an image consisting of a series of lines by homopolymerizing thediacetylene cinnamate monomer in the corresponding discrete areas ofexposure. The image is instantly visible as magenta lines on a colorlessnon-exposed monomer background. After about 1 hour, in the same manner,dots between the magenta lines are inscribed on the film with theelectron beam scriber to provide a magenta image of lines and dots onthe unexposed colorless background Also in Part D, a broad exposure ofthe entire film is made with the copper vapor laser instead of impingingdiscrete areas. Within a fraction of a second the well defined image ofthe magenta lines and dots is transformed to a permanent bright yellowimage.

                  TABLE I                                                         ______________________________________                                        Comparison of Diacetylene Diether Products                                              UV Exposure*  heat                                                  Example   Sensitivity/Color                                                                           Permanent Color                                       ______________________________________                                        1         high/purple   red                                                   2         high/blue     red                                                   3         high/pink     intense golden yellow                                 4         high/purple   red                                                   5         high/magenta  intense golden yellow                                 6         low/pale yellow                                                                             --                                                    7         low/magenta   --                                                    8         inactive**    --                                                    9         inactive**    --                                                    10        inactive**    --                                                    ______________________________________                                         *a mercury lamp, Mineralight ®, Model USV54 operating at about 254 nm     wavelength                                                                    **no observable color after 30 seconds                                   

It is to be understood that many modifications and substitutions can bemade in the above examples without departing from the scope of thisinvention. For example, any of the other monomers or homopolymers ofdiacetylene ethers described herein can be substituted in any one of thecorresponding examples to prepare films which upon imaging, provide adesired pattern or data recording in high acuity and sharp contrast.Further, any of the other radiation devices which transmit energy in ashort wavelength of 200-350 nm and/or any of the lasers which transmitenergy in the longer wavelength above 350 nm can be substituted in anyof the corresponding examples in accordance with the teachings of thisinvention. Also any of the energy absorbing heat transmitting dyesincluding other polycarbocyamine dyes, squarilium or pyrilium dyes anddye complexes or mixtures mentioned or described in copending U.S.patent application Ser. No. 07/601,532, filed concurrently herewith, andin U.S. Pat. No. 4,513,071, which absorb energy in a wavelength similarto that of the energy generated from the laser, can be substituted inthe appropriate examples or examples indicated by the abovesubstitutions. Additionally, any of the other photoresist coatings foran image receiving device can be made without departing from the scopeof this invention.

What is claimed is:
 1. An imageable film comprising a substrate on whichis supported an imageable layer of the diacetylene ether having theformula ##STR6## wherein X is a radical having from 1 to 22 carbon atomsand is selected from the group of alkyl, carbamate, alkenyl, aryl,phenylamino, alkaryl, aralkyl, aralkenyl, monoalkylamino anddialkylamino and Y is alkyl or alkenyl having from 1 to 22 carbon atomsor --CH₂ OCH₂ CH₂ OOCX' where X' is independently selected from thegroup of X.
 2. The film of claim 1 in which X of said diacetylene etheris alkyl, carbamate, phenyl or styryl and Y is --CH₂ OCH₂ CH₂ OOCX'. 3.The film of claim 1 in which said diacetylene ether has the symmetricalstructure

    XCOOCH.sub.2 CH.sub.2 OCH.sub.2 C.tbd.C--C.tbd.CCH.sub.2 OCH.sub.2 CH.sub.2 OOCX.


4. The film of claim 1 in which said diacetylene ether is a mixture ofsaid diacetylene ether compounds.
 5. The film of claim 1 in which saiddiacetylene ether has the formula

    [C.sub.3 H.sub.7 NHCOOC.sub.2 H.sub.4 OCH.sub.2 C.tbd.C].sub.2.


6. The film of claim 1 in which said diacetylene ether has the formula

    [(CH.sub.3).sub.2 CHNHCOOC.sub.2 H.sub.4 OCH.sub.2 C.tbd.C].sub.2.


7. The film of claim 1 in which said diacetylene ether has the formula

    [CH.sub.3 NHCOOC.sub.2 H.sub.4 OCH.sub.2 C.tbd.C].sub.2.


8. The film of claim 1 in which said diacetylene ether has the formula

    [C.sub.6 H.sub.5 --NHCOOC.sub.2 H.sub.4 OCH.sub.2 C].sub.C.sub.2.


9. The film of claim 1 in which said diacetylene ether has the formula

    [C.sub.6 H.sub.5 COOC.sub.2 H.sub.4 OCH.sub.2 C.tbd.C].sub.2.